Polymer treatment

ABSTRACT

A process for the separation of volatile material from particulate polymer which has been substantially freed from unreacted monomer in an earlier separation step, comprising (a) feeding the particulate polymer to a purge vessel, optionally causing it to move through the vessel in substantially plug-flow mode, (b) heating the particulate polymer in the purge vessel to a temperature grater than 30° C. but insufficiently high to cause the particles to become agglomerated, and/or maintaining the polymer at a temperature in this range in the purge vessel, (c) feeding gas to the purge vessel counter-current to the movement of the particulate polymer to remove volatile material therefrom, (d) removing the particulate polymer from the purge vessel, wherein substantially all of the heating of the particles which occurs in the purge vessel is accomplished by preheating the gas fed into the purge vessel.

The present invention relates to a process for the removal of volatilematerial from particulate polymer, and more especially to the removal oftraces of volatile constituents from pelletised polymer, polymer powderor granular polymeric material.

Whilst the present invention can in principle be applied to anyparticulate polymer for the removal of volatiles therefrom, thefollowing description refers primarily to the application of the processto the removal of volatiles from particulate polyolefins.

Polyolefins prepared by catalytic polymerisation or copolymerisation ofolefins, for example, ethylene, propylene or higher olefins such as C₄to C₁₂ alpha-olefins, are generally subjected to a process for removalof the bulk of the unreacted monomer before being processed into usefularticles. Such processes for removal of unreacted monomer generallyinvolve a monomer separation and recovery procedure wherein the bulk ofthe unreacted monomer associated with the polyolefin product isseparated therefrom when the polyolefin is first removed from thepolymerisation reactor. Processes for this initial monomer separationand recovery depend on the particular technology being employed for thepolymerisation reaction. For example, in the gas phase(co)polymerisation of olefins, the polyolefin product is normally a finepowder fluidised by, or stirred in, an atmosphere comprising the gaseousmonomer(s). Monomer may be separated and recovered from the gas phaseprocess, for example, by isolating a continuous stream of particulatepolymer product associated with at least some gas, and optionally someliquid, comprising unreacted monomer; reducing the pressure andrecycling the volatile components to the reactor; and purging thepolymer component with inert gas, for example, nitrogen or carbondioxide.

Thus the volatile materials referred to throughout this specificationcan be, for example, the monomer or monomers themselves, oligomers, anysolvent or diluent used in the polymerisation, the catalyst materials orproducts derived therefrom, additives in the polymerisation (e.g.molecular weight regulators), impurities present in any of the materialsused in the polymerisation, or materials employed for lubricating movingparts of the reactors. Such volatile substances can also arise fromdegradation or inter-reaction of the polymerisation componentsthemselves and/or their products. The presence of such volatilesubstances in the final polymer is generally undesirable and can result,for example, in unwanted odour in articles manufactured therefrom, orcan produce taint in foodstuffs packed in containers fabricated from thepolymer, or in water from potable water piping systems. The presence ofinflammable volatile materials can also present a fire or explosionhazard. Likewise, such volatile materials can have toxic, irritant orother undesirable pharmacological properties which normally render theirremoval desirable or even essential.

The production of volatile substances in the polymer can also occurduring pelletisation of the polymer, for example, by thermal degradationof the polymer itself, or by the degradation of additives employed inthe pelletising process.

GB-A-1272778 relates to a process for the removal of volatileconstituents from particulate olefin polymers which have been producedby the gas phase polymerisation of the monomers for example of ethyleneor propylene, by treating a layer of the polymer, whose particles have amean diameter of from 10 to 5000 microns, with a stream of inert gas ata temperature of from at least +80° C., to at least 5° C. below thecrystallite melting of the polymer in the treatment zone while keepingthe layer in vigorous motion.

EP-A-0047077 relates to a process for removing unpolymerised gaseousmonomers from solid olefin polymers by conveying the polymer (e.g. ingranular form) to a purge vessel, contacting the polymer in the purgevessel with a countercurrent inert gas purge stream to strip away themonomer gases which are evolved from the polymer, and recycling aportion of the resulting inert gas-monomer gas stream to the purgevessel.

The present invention is concerned with an improved method for theremoval of traces of volatile material, e.g. unreacted monomer,oligomers or other volatile constituents such as solvent or degradationproducts, from particulate polymeric materials, especially polymersprepared by the catalytic polymerisation of organic monomers.

In particular, the present invention is concerned with removal ofvolatile materials from particulate polymeric materials, preferablyparticulate polyolefins, which have previously been subjected to atleast one process for separation of the unreacted monomer, for example,by processes such as those described in GB-A-1272778 and EP-A-047077.

The present invention provides a process for the separation of volatilematerial from particulate polymer which has been substantially freedfrom unreacted monomer in an earlier separation step, comprising

(a) feeding the particulate polymer to a purge vessel and causing it tomove through the vessel in substantially plug-flow mode,

(b) heating the particulate polymer in the purge vessel to a temperaturegreater than 30° C. but insufficiently high to cause the particles tobecome agglomerated, and/or maintaining the polymer at a temperature inthis range in the purge vessel,

(c) feeding gas to the purge vessel to remove volatile materialtherefrom, removing the particulate polymer from the purge vessel,

wherein substantially all of the heating of the particles which occursin the purge vessel is accomplished by preheating the gas fed into thepurge vessel.

By “plug flow mode” is meant throughout this specification that the flowof particulate polymer through the relevant vessel occurs in such amanner that there is little or no axial mixing as the particulatepolymer travels through the vessel, thus ensuring that the residencetime of the particles is substantially uniform. “Plug flow” is sometimesreferred to in the art as “mass flow”, especially where the flow underconsideration is movement of solid particulate materials. An alternativedefinition is that the flow characteristics of the particulate polymerin the purge vessel are such that the standard deviation of theresidence time is preferably not greater than 20%, and even morepreferably not greater than 10% of the mean residence time of theparticulate polymer in the purge vessel.

Preferably the gas fed to the purge vessel is fed counter-current to themovement of the particulate polymer.

The particulate polymer from which it is desired to remove volatilematerial can be, for example, polymer powder, pelletised polymer orgranular material which has already been subjected to a primary monomerseparation step. In the case that the particulate polymer has beenprepared in the presence of a transition metal-containing catalyst,preferably any catalyst residues present in the polymer have beendeactivated prior to treating the polymer in accordance with the processof the present invention. Preferably the particulate polymer ispolyolefin powder, pellet or granular material having been prepared bypolymerisation or (co)polymerisation of one or more monomeric 1-olefins,in the gas phase, the liquid phase (e.g. using so-called “particle form”polymerisation conditions), or the solution phase, or from the hightemperature high pressure process (often referred to as the “highpressure process”). Alternatively, the particulate polyolefin can bepolyolefin which has been converted into another particulate form, e.g.by granulation or pelletising. Preferably the particulate polyolefin isa pelleted polymer, more preferably a pelleted polyolefin. Accordinglyit is also preferred that prior to entry into the purge vessel, theparticulate polyolefin has passed through an extruder to be pelletised.

The quantity of volatile material (excluding water) present in thepolymer fed to the purge vessel, as measured by chromatography (KWSmethod, carbon-hydrogen chromatography), is preferably not greater than500 ppm (parts per million by weight), more preferably not greater than300 ppm, and even more preferably not greater than 100 ppm. The quantityof volatile material (excluding water) present in the polymer leavingthe purge vessel after treatment according to the invention, as measuredby chromatography (KWS method, carbon-hydrogen chromatography), ispreferably not greater than 300 ppm (parts per million by weight), morepreferably not greater than 200 ppm, and even more preferably notgreater than 100 ppm. The reduction in the quantity of volatile material(excluding water) present in the polymer leaving the purge vessel aftertreatment according to the invention compared with that entering thepurge vessel, as measured by chromatography (KWS method, carbon-hydrogenchromatography), is greater than 300 ppm (parts per million by weight),more preferably greater than 500 ppm.

This significant reduction in volatile material content has asignificantly beneficial effect on the organoleptic properties of thefinal polymer. The invention can reduce the taste rating of a highdensity polyethylene according to the KTW method from 2-3 down to 1-1.5.

The particulate polymer fed to the purge vessel can be preheated beforeentering the purge vessel, or can be heated solely in the purge vesselitself. The particulate polymer can be fed to the preheating vesselintermittently, continuously, as a batch or in batches. Preferably it isfed continuously. Preferably the particulate polymer moves through thepreheating vessel in substantially plug-flow mode. The temperature towhich the particulate polymer is heated in the preheating vessel may beat least 30° C., and up to 70° C. or higher, provided that thetemperature is insufficiently high to cause the particles to becomeagglomerated. As a rough guide, the temperature should not be greaterthan about 5° C. below the Vicat softening temperature. The particulatepolymer is preferably fed to the heating vessel using a pneumaticconveying technique. If a preheating vessel is employed, it can, ifdesired, be provided with means to pass a purge gas countercurrent tothe movement of the particulate polymer through the vessel. If desired,hot gas, e.g. hot nitrogen, can be used to heat the particulate polymerin the preheating vessel. Alternatively the preheating vessel is heatedusing conventional industrial equipment, for example, steam or hot waterjacketing.

In the case that the particulate polymer is pelletised, the pellet can,if desired, be fed directly from the pelletising machine to the purgevessel, or to the heating vessel if one is employed. Feeding pellet tothe purge vessel or to the heating vessel direct from the pelletisingmachine can make further savings in energy requirements, especially ifthe pellet discharge from said machine still contains residual heat fromthe pelletising process. This saving in energy can be optimised, forexample, by suitable adjustment of the temperature of the quench watersuch that the pellet remains relatively hot after the quench, but not sohot that agglomeration of the pellets can occur.

The particulate polymer is fed to the purge vessel in any convenientmanner, for example, using pneumatic conveying or by means of gravityfeed devices employing suitable feeder valve means between the sourceand the purge vessel. It is preferred to feed the particulate polymercontinuously to the purge vessel.

The residence time of the particles in the vessel is substantially thesame for all the particles. Plug flow can be achieved using conventionalindustrial equipment. Thus it is preferred to employ a purge vessel withsmooth internal walls and having uniform cross section throughout amajor portion of its length. A frusto-conical or other tapering crosssection, for example, at the exit of the purge vessel, can be usedprovided that the angle of the discharge cone is calculated so as toensure the plug flow qualities of the vessel (the angle can becalculated from shear test results, and depends on the nature of theparticulate polymer being treated). The principles of plug flow are wellknown in the art and suitable apparatus can be readily designed adoptingthese principles. The purge vessel is preferably tubular and ofsubstantially uniform cross section. The major portion may take theform, for example, of a tube having square or circular cross section.The purge vessel is most preferably a vertically disposed cylindricalvessel having a conical section at the base which tapers towards anoutlet for the polymer located at the bottom of the vessel. Preferablythe purge vessel is vertically disposed. Most preferably the purgevessel is of uniform cylindrical cross section throughout a major partof its length, and has a length at least twice its diameter in order tohelp ensure plug flow.

In one embodiment plug flow is achieved in a cylindrical vessel byselection of a particular valve to control the discharge opening. Thevalve is in the form of an upturned cone seated on a frustoconical seat,thereby defining an annular passageway when the valve is open. Such anarrangement can prevent rapid discharge of polymer through the centre ofthe purge vessel, which may result in non-plug flow. When operating withsuch an arrangement, it is preferred that the valve is not continuouslyopen, but does so intermittently; this has been found to be best toensure plug flow. Preferably the valve is open half the time; a typicalcycle is 1-3 minutes open, with the same amount of time closed, althoughthe exact time will of course depend on the size of the vessel.

The rate of flow and the dimensions of the purge vessel are suitablyarranged so that the residence time of the particulate polymer in thepurge vessel lies in the range from about 0.5 to 16 hours, preferably 2to 16 hours, more preferably 6 to 12 hours. For certain applications, atleast 10 hours is required.

The temperature to which the particulate polymer is heated in the purgevessel is suitably at least 30° C., preferably at least 50° C., mostpreferably at least 70° C. or higher, provided that the temperature isinsufficiently high to cause the particles to become agglomerated. Asmentioned above, as a rough guide, the temperature is preferably notgreater than about 5° C. below the Vicat softening temperature. Forexample, if the Vicat softening temperature is 80° C., the maximumtemperature to which the particulate polymer is heated should preferablynot be greater than 75° C. In the case that the particulate polymer ishigh density polyethylene having a density of at least 0.945 kg/m³, thetemperature of the heating in the purge vessel is preferably in therange 70 to 100° C. On the other hand, in the case that the particulatepolymer is a lower density copolymer, for example, a copolymer ofethylene with a higher 1-olefin, e.g. having a density in the range0.915 to 0.945 kg/m³, the said temperature preferably lies in the range60 to 80° C. In any event the temperature must be insufficiently high tocause the particles to become agglomerated. Failure to observe this canresult in the polymer becoming blocked in the preheating or purgevessels, or even forming an intractable mass within these vessels.

The particulate polymer may be moved through the purge vessel using anysuitable means of motivation, for example using an Archimedean screwdevice or merely under the influence of gravity. Preferably however theparticulate polymer moves under the influence of gravity in response tothe discharge of solid from the base of the purge vessel. Preferably thepurge vessel is insulated to retain heat during purging.

Gas is preferably passed through the purge vessel counter current to theflow of the particulate polymer therein. By “counter current” is meantthat the gas is passed across or against the flow of the particles. Thegas is heated prior to injection into the purge vessel. Normally the gasis air. However if desired the air can be supplemented with another gasor gases, for example, nitrogen or carbon dioxide, e.g. if it is desiredto reduce any potential risk of fire or explosion. However, the presentinvention is generally applied to the reduction of volatiles inparticulate polymer in which the content of volatiles is already at arelatively low level. Accordingly, the level of volatiles present in thepurge gas stream exiting from the purge vessel is normally not more thanabout 5 milligrams per litre of gas, preferably not more than about 1milligram per litre of gas. A particularly preferred level is less than150 g/m³.

The rate of flow of gas through the particulate polymer is maintained ata level below that which would cause disruption of the plug flow of theparticulate polymer. This is well below the rate of flow which wouldcause fluidisation of the particulate polymer. In the case of pelletedpolymer, the rate of flow of gas that can be tolerated before the onsetof disruption of the plug flow is generally substantially higher thanfor powdery polymer. In order to provide sufficient heating of thepolymer, the rate of flow of gas is preferably at least 80 litres perhour per square centimetre of cross section measured radially across thedirection of flow of particulate polymer through the purge vessel (unitshereinafter abbreviated to l.hr⁻¹ cm⁻²). The maximum flow rate which canbe tolerated without disruption of the plug flow is about 150 l.hr⁻¹cm⁻².

Although all of the gas may be introduced into the purge vessel close toits bottom and blown upwards through the particulate polymer, thisrequires the use of significant pressure. We have found that removal ofvolatiles can be just as effective if the majority of the hot gas isintroduced into the purge vessel close to the top where the particulatepolymer enters, with only a relatively small proportion of the gas beingintroduced at the bottom. Introducing gas close to the top of the vesselrequires a much lower pressure, as of course does introducing a muchsmaller mass flow of gas at the bottom. It is believed that thisarrangement is just as effective because once the polymer is heated,only a relatively small air flow across it is required in order toremove the volatile compounds. Thus the most efficient means ofachieving hot particulate polymer having a flow of gas across it is tointroduce the majority of the gas required to keep the polymer close tothe top of the vessel. Accordingly it is preferred that at least aportion of the gas entering the purge vessel does so that one or morepoints close to the top of the purge vessel; and it is preferred thateach of said one or more points are located at a level such that lessthen 20% of the volume of particles in the vessel lie above that levelwhen the vessel contains the maximum quantity of particulate polymer. Itis also preferred that no more than 20%, more preferably no more than10% of the total mass of gas entering the vessel does so close to thebottom of the vessel. In this case, the rate of flow of gas entering theclose to the bottom of the vessel is typically at least 0.5 litres perhour per square centimetre of cross section measured radially across thedirection of flow of particulate polymer through the purge vessel (unitshereinafter abbreviated to l.hr⁻¹ cm⁻²). Thus for example, rates of flowof gas from 2 to 10 l.hr⁻¹ cm⁻² entering at the bottom of the purgevessel are particularly useful. It is also preferred that a portion ofthe gas introduced close to the top of the purge vessel is dischargeddirectly into the middle of the vessel, optionally through an axiallyextending conduit. This helps to avoid cold spots in the centre of thevessel. Preferably the mass flow of gas introduced directly into themiddle of the vessel is about 20-40%, typically approximately one-third,that introduced into the side of the vessel at the same level.Generally, it will be understood that the precise location of gas entrypoints, gas flowrates at each entry point and also purge vesseldimensions are calculated in each individual case depending on theparticulate polymer being treated, and the flowrate of the polymer, soas to obtain a uniform gas distribution and efficientheating/devolatilising.

Whilst substantially all of the heating of the particulate polymer iscaused by the hot gas, the invention does not exclude the possibility ofsome auxiliary heating means being present, such as a heat exchangerpositioned centrally near the top of the purge vessel so as to ensureadequate heating at the centre of the vessel.

The pressure in the purge vessel can be any desired pressure, but inpractice the use of a pressure close to atmospheric pressure (e.g.slightly above 1 bar absolute but less than 200 mbarg) is generallysatisfactory as this avoids the need to use expensive pressure vesselsand blowers. In practice the introduction of the purge gas into thepurge vessel will generally cause a slight increase of pressure therein.

Volatile materials diffuse from the particulate polymer in the purgevessel into the gas stream and are carried counter current to themovement of the particulate polymer towards the region where theparticulate polymer is fed to the vessel. The gas is preferably ventedfrom the purge vessel using suitable piping means. The vented gascontaining the volatiles can be fed to a flare stack or, if it isdesired to recover any volatile components, for example, it may be fedto a suitable recovery unit. Frequently it is found that theconcentration of volatiles is so small (less than 150 mg/m³) that thegas from the purge vessel can be vented direct to the atmosphere.Preferably the process conditions are maintained such that theconcentration of any inflammable volatile materials in the gas ventedfrom the purge vessel provide less than 25%, preferably less than 5% ofthe flammability limit of the gas. The concentration of such volatilematerials can be reduced, for example, by reducing one or more of thefollowing: (1) the standing volume of particulate polymer in the purgevessel, (2) the rate of flow of the particulate polymer through thepurge vessel and (3) the temperature of the particulate polymer in thepurge vessel: or by increasing the rate of flow of the gas through thepurge vessel.

The particulate polymer is suitably removed from the purge vessel simplyby force of gravity. However this may be assisted by conventionalindustrial conveying means for particulate materials, for examplemotorised valves or a rotary airlock. Preferred mechanical withdrawalmeans include variable rate withdrawal means, for example, variablespeed motorised valves or motorised screws. The vessel is preferablyequipped with means to detect the quantity or level of particulatepolymer therein, for example a means to detect the level of settledparticulate polymer in the vessel. Preferably the means to detect thequantity or level of particulate polymer within the vessel is coupledwith the variable rate withdrawal means, for example, to maintain aconstant volume of particulate polymer within the vessel. The couplingmay be achieved, for example, by electronic means or mechanical means.

After the particulate polymer has passed through the purge vessel it isnormally still hot and may require cooling before being transferred tostorage or undergoing further treatment or processing. For example, inthe case of polyethylene, if it is desired to transfer the particulatepolymer to storage using dilute or dense phase pneumatic conveyingmeans, it is preferred to cool it to a temperature below about 65° C.,typically 40-60° C., before transfer to reduce the possibility of socalled “angel hair” forming in the pneumatic conveying lines. The meansused to cool the particulate polymer, if any, can comprise, for example,conventional industrial particulate cooling equipment. Air or watercooling may be used. For example, the hot particulate polymer can be fedto a gas fluidised bed cooler operating under batch or continuousconditions. Air used for cooling can subsequently be introduced into thefeed of the hot air to be introduced into the purge vessel in order toreduce heating costs.

In one embodiment, the cooling means can be incorporated at the bottomof the purge vessel in order to save on equipment costs; in this case,the design must be such so as to ensure plug flow throughout the purgevessel at least until entry into the cooling portion. Optionally, thegas introduced into the purge vessel to remove volatile materials isinitially passed unheated through the bottom of the vessel, where itassists in cooling the hot particulate polymer whilst at the same timebeing heated. This gas is then further heated to the requiredtemperature, and then reintroduced into the purge vessel at the desiredlocation to contact the polymer.

As has been indicated above, it is preferred to withdraw particulatepolymer from the purge vessel using means to withdraw the polymercontinuously. Likewise, the preheating vessel and/or the cooling vesselare preferably equipped with means to withdraw the polymer continuously,for example using motorised valves or motorised screws. Preferably thewithdrawal means are variable rate withdrawal means, for example, usingvariable speed motorised valves and/or a vibrating table. The vessel(s)is/are preferably equipped with means to detect the quantity or level ofparticulate polymer therein, for example a means to detect the quantityor level of settled particulate polymer in the vessel(s). Preferably themeans to detect the quantity or level of particulate polymer within thevessel(s) is coupled with the variable rate withdrawal means, forexample, to maintain a constant volume of particulate polymer within thevessel(s). The coupling may be achieved, for example, by electronicmeans or mechanical means.

If desired, the flow of particulate polymer through the cooling vesselcan also be plug flow mode. Plug flow of the particulate polymer throughthe cooling vessel can be achieved by standard industrial means.

Particulate polymer suitably employed in the present invention can be,for example, polymer powders which are the direct products ofpolymerisation processes, provided that such polymer powders have beensubstantially freed from unreacted monomer in an earlier separationstep, for example, the powder produced from gas fluidised bedpolymerisation of olefins or from particle form processes forpolymerising monomers in a liquid diluent. Preferred polymer particlesare polymer pellets which are well known in the art as a standardproduct employed for the fabrication of polymeric articles. The size ofthe polymer particles is suitably in the range 0.1 to 10 mm, preferablyin the range 2 to 7 mm. For example, polymer pellets employed in thefabrication of plastics articles generally lie in the range 3 to 6 mm.

Preferably the polymer particles comprise one or more polyolefins.Preferred polyolefins are polyethylene, polypropylene, and copolymers ofethylene with one or more C₃ to C₁₂ alpha olefins. Examples of suchpolymers are high density polyethylene, medium density polyethylene,linear low density polyethylene and very low density polyethylene(VLDPE).

In one embodiment of the invention, the above process is performedsubsequent to a treatment step for reducing the amount of gaseousdiluent contain within the raw polymer slurry discharged from thepolymerisation reactor. When discharged from the polymerization reactor,raw polymer slurry is in the form of a material containing significantamounts of diluent, smaller amounts of unreacted olefinic monomer(s) andwhich may contain small amounts of catalyst, cocatalyst, otherhydrocarbons and any other material depending on the manufacturingprocess used (hereafter called under the collective term“contaminants”). After the pressure release, the raw polymer resin ispassed into the above mentioned purge bin at about atmospheric pressure,where nitrogen is used to purge these contaminants out. The purge ventstream from this step contains nitrogen, diluent, olefinic monomer, andother process-specific materials. In order to minimise the amount ofdiluent transferred from an olefin polymerization reactor to ahydrocarbon purge bin and, optionally, to maximise recovery of saiddiluent from the purge bin, the following steps are carried out:

-   continuously discharging from the polymerisation reactor a slurry    comprising polyolefin and diluent;-   submitting said slurry to a pressure release such that the diluent    is evaporated and a polyolefin/gas mixture is formed;-   continuously discharging said polyolefin/gas mixture into a    collecting vessel;-   opening the intake valve of a concentrator vessel comprising also a    discharge valve in such a way that a predetermined volume of said    polyolefin/gas mixture is transferred into said concentrator vessel;-   closing the intake valve of the concentrator vessel;-   opening the discharge valve of said concentrator vessel in such a    way that said polyolefin/gas mixture is transferred into the    hydrocarbon purge bin.    An advantage of the above sequence of steps is that, instead of    transferring the polyolefin/gas mixture directly from the    polymerization reactor—respectively directly from the collecting    vessel—to the purge bin together with a significant quantity of gas    from the polymerization reactor, a concentrator vessel is used    between the polymerization reactor respectively between the    collecting vessel and the purge bin. The quantity of gas transferred    from the polymerization reactor to the purge bin is thus minimized.    Usually, the polymerization reactor is under high pressure (10-40    bars) whereas the purge bin is at a pressure close to the    atmospheric pressure. The less effluent gas is taken out of the    collecting vessel, the less gas must be recycled and pressurized to    the higher pressure required in the polymerization reactor. The use    of the concentrator vessel as described above allows to decrease the    quantity of gas that is transferred to the low pressure side i.e. to    the purge bin. For instance, when isobutane is used as diluent for    the polymerization and when the pressure in the second step of the    process of the invention drops to about 10 bar, the quantity of gas    transferred to the purge bin is reduced to about 2.5 weight %.    Consequently the compressors can be of smaller size, they are thus    less costly to buy and to operate. Furthermore, since the quantity    of unreacted monomer and solvent that must be recycled is smaller,    the downstream recycling equipment may be smaller and less    energy-consuming.    A preferred option is that instead of using one concentrator vessel,    two concentrator vessels are used in parallel.    In the first part of the cycle, the first concentrator vessel is    filled with the polyolefin/gas mixture and the intake valve of the    first concentrator vessel is closed. Before the first concentrator    vessel is emptied into the purge bin, a pressure compensation valve    connecting the two concentrator vessels is opened. Gas contained in    the first concentrator vessel is transferred to the second    concentrator vessel until the pressure in the two concentrator    vessels is about the same. The pressure compensation valve between    the concentrator vessels is then closed and the first concentrator    vessel is emptied into the purge bin. The pressure inside the first    concentrator vessel drops to the pressure inside the purge bin    whereas the pressure in the second concentrator vessel is higher    than the pressure inside the purge bin but lower than the pressure    in the collecting vessel, i.e. about 30-50% lower.    In the second part of the cycle, the second concentrator vessel will    be filled with the polyolefin/gas mixture from the collecting vessel    and the pressure between the two concentrator vessels is    equilibrated by opening the pressure compensation valve connecting    the two concentrator vessels. The second concentrator vessel will    eventually be emptied into the purge bin.    The method using two concentrator vessels in parallel reduces the    quantity of gas transferred from the polymerization    reactor—respectively form the collecting vessel—to the low pressure    side i.e. to the purge bin still further. For instance, when    isobutane is used as diluent for the polymerization and when the    pressure in step (b) drops to about 10 bar, the quantity of gas    transferred to the purge bin is reduced to about 1 weight %. These    figures depend on the bulk density of the polymer and on the density    of the gas. A further option includes the following steps to treat    the purge vent stream from the purge bin:-   compressing and cooling a purge vent stream from a purge bin,    resulting in partial condensation of the stream, thereby dividing    the stream into a condensed portion enriched in monomer and an    uncondensed portion enriched in purge gas;-   dividing the uncondensed portion into two parts,-   recirculating the first part of the uncondensed portion to the purge    bin;-   treating the second part of the uncondensed portion in a separation    unit, to create a more-enriched purge gas stream and a mixed stream;-   recirculating the enriched purge gas stream from the separation unit    at the bottom or at an intermediate level of the purge bin and-   recirculating the mixed stream from the separation unit to the    condensation step, by returning them to the purge vent stream    upstream of the compression.    The process for treating the purge vent stream is very economical.    Indeed, since the quantities and the concentration of monomers and    other recyclable products coming from the purge bin are smaller than    in traditional processes, the equipment, i.e. the    compression/cooling and separation units need not be very large.    They are less costly to buy and to operate.    Furthermore, to recycle the first part of the uncondensed portion    directly to the purge bin further reduces the size, costs and energy    consumption of the equipment.    The condensation step is preferably carried out at a pressure    comprised between about 8 to 20 bar; when isobutane is used as    diluent for the polymerization, said pressure is typically comprised    between 12 and 16 bar. The condensation step is preferably further    carried out at a temperature comprised between −30 and +50° C.; when    isobutane is used as diluent for the polymerization, said    temperature is typically comprised between 5 and 15° C.    The separation unit may comprise a membrane separation unit, a    cryogenic separation unit, an absorption unit, etc. In the case of a    cryogenic separation, the unit comprises a distillation column with    a condenser operating at low temperature, for instance in the range    of −50 to −100° C.    The separation by means of a membrane is preferred. It is preferably    carried out by using a membrane that has a selectivity for the    faster permeating component—i.e. the olefin—over the other    component—i.e. the purge gas—of at least about 5.    It should be noted that the above process for minimizing the    quantity of gas which is transferred from a polymerization reactor    to a hydrocarbon purge bin, can be applied to any polymer    manufacturing operation.

The present invention will now be illustrated with reference to theaccompanying drawings wherein FIG. 1 represents diagrammatically a firstembodiment of apparatus for reducing the volatiles content of linearhigh density polyethylene (HDPE) pellets prepared from HDPE powder madeby the gas phase fluidised bed polymerisation of ethylene.

FIG. 1 shows a purge vessel 1, to which is fed from an extruder (notshown) a continuous stream of pellets via inlet pipe 3, with any excessbeing transferred to a buffer silo via line 5. In this particularexample, the pellets are introduced at a rate of 6 tonnes/hour, andpurge vessel 1 has a diameter of 4.5 m and an internal volume of 150 m³.Hot air from line 14 is introduced at points 12, having been heated bysteam from line 16. This air blows upwards through the mass of pellets,and maintains the temperature inside the purge vessel at 90° C. Plugflow is ensured by the discharge valve, which is in the form of anupturned cone. In this particular embodiment, the valve is notcontinuously open, but instead opens and closes for 2 minutes at a time.It was found that in this arrangement such a regime ensured plug flow.The treated pellet discharges into hopper 18 and thence into a coolingvessel 20, which is cooled to 40-60° C. by water from line 22. Finally,the cooled pellets are discharged into an air conveyor line 24.

In FIG. 2 a similar arrangement is shown, with a purge vessel 1, fedcontinuously from an extruder via inlet pipe 3. In this example the rateof pellet feed is 30 tonnes/hour, and the purge vessel 1 has a greaterinternal volume of 700 m³, and a different system of both discharge andhot air input. Hot air from line 14, heated by steam from line 16, isintroduced at separate points 12 and 13. In this particular example, therelative rates of input are 17 kg/s at point 12 and 1 kg/s at point 13.It should be noted that points 12 and 13 are representative of a numberof inlets, typically 3-5, spaced around the diameter of the purge vesselat the same level. Introducing the major proportion of hot air at point12 ensures that the pellets are satisfactorily heated when as they enterthe purge vessel; further inlets can be provided to introduce hot airinto the centre of the vessel at the same level so as to ensurehomogeneous heating. It has been found that introducing a substantialflow of air at the top of the vessel means that only a small flow isrequired at the bottom at point 13, where a relatively greater pressureis required. As in the example of FIG. 1, the temperature inside thepurge vessel is maintained at 90° C. Residence time for HDPE pellets istypically 10-12 hours. The manner of discharge from the vessel 1 is alsodifferent from that of FIG. 1. Instead of an internal valve arrangement,there is a continuous discharge through opening 17, with plug flow beingensured by calculation of the dimensions and angle of tapered portion 15of the purge vessel. As before, the treated pellet discharges into acooling vessel 20, which is cooled to 40-60° C. by water from line 22.The cooled pellets are then discharged into an air conveyor line 24.

EXAMPLE 1

The process as described above in connection with FIG. 1 was conductedon a a stream of pellets of high density polyethylene. Table 1 belowshows the content of volatile material (excluding water) present in thepolymer entering the purge vessel, and the content leaving it aftertreatment according to the invention, as measured by chromatography (KWSmethod on pellets, carbon-hydrogen chromatography at 200° C. up to C16).It can be seen that a significant reduction in volatile material contentis achieved by the process of the present invention: a reduction of over500 ppm is possible. TABLE 1 volatile material content Before Aftertreatment treatment Reduction (ppm) (ppm) (ppm) 546 195 351 496 89 407550 94 456 646 98 548 732 143 589 601 122 479 456 83 373 532 90 442 543172 371 621 114 507 649 143 506 564 121 443 552 116 436 474 142 332

1. A process for the separation of volatile material from particulatepolymer which has been substantially freed from unreacted monomer in anearlier separation step, comprising (a) feeding the particulate polymerto a purge vessel and causing it to move through the vessel insubstantially plug-flow mode, (b) heating the particulate polymer in thepurge vessel to a temperature greater than 30° C. but insufficientlyhigh to cause the particles to become agglomerated, and/or maintainingthe polymer at a temperature in this range in the purge vessel, (c)feeding gas to the purge vessel to remove volatile material therefrom,removing the particulate polymer from the purge vessel, whereinsubstantially all of the heating of the particles which occurs in thepurge vessel is accomplished by preheating the gas fed into the purgevessel.
 2. Process according to claim 1 wherein the gas is fed to thepurge vessel counter-current to the movement of the particulate polymer.3. Process according to claim 1, wherein at least a portion of the gasfed to the purge vessel enters the vessel at one or more points locatedcloser to the top of the vessel than to the bottom.
 4. Process accordingto claim 3 wherein at least 80% of the total gas flow entering thevessel does so at said one or more points located closer to the top ofthe vessel.
 5. Process according to claim 4 wherein said one or morepoints located close to the top of the vessel are located at a levelsuch that less than 20% of the volume of particles in the vessel lieabove that level when the vessel contains the maximum quantity ofparticulate polymer.
 6. Process according to claim 1 wherein no morethan 20% of the total mass of gas entering the vessel does so at closeto the bottom of the vessel.
 7. Process according to claim 1 wherein nomore than 10% of the total mass of gas entering the vessel does so atclose to the bottom of the vessel.
 8. Process according to claim 1wherein part of the gas entering the purge vessel is discharged directlyinto the middle of the vessel at the same level as the point of entry ofthe gas entering at one or more points located closer to the top of thevessel.
 9. Process according to claim 8, wherein the mass flow of gasdischarged directly into the middle of the vessel is 20-40% of thatdischarged into the side of the vessel at the same level.
 10. Processaccording to claim 1, wherein the particulate polymer is in the form ofpellets.
 11. Process according to claim 1 wherein the discharge from thepurge vessel comprises a frustoconical portion having an opening at itsbottom, on which portion is seated a valve in the form of an upturnedcone, thereby defining an annular passageway when the valve is open. 12.Process according to claim 11 wherein discharge through said valve isintermittent due to opening and closing of the valve.
 13. Processaccording to claim 1, wherein at least a portion of the gas fed to thepurge vessel is at least partially preheated using heat from theparticulate polymer.
 14. Process according to claim 13, wherein saidportion of the gas fed to the purge vessel is preheated by passing itthrough the purge vessel prior to contacting it with the particulatepolymer.